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      "text": "Li and Mn rich (LMR) layered oxides, written as x Li2MnO3 \u0001 (1 \u0000 x )LiMO2 (M = Mn, Ni, Co, Fe, etc.), have been widely reported in recent years due to their high capacity and high energy density. The stable structure and superior performance of LMR oxides make them one of the most promising candidates for the next-generation cathode materials. However, the commercialization of these materials is hindered by several drawbacks, such as low initial Coulombic efficiency, the degradation of voltage and capacity during cycling, and poor rate performance. This review summarizes research progress in solving these concerns of LMR cathodes over the past decade by following three classes of strategies: morphology design, bulk design, and surface modification. We elaborate on the processing procedures, electrochemical performance, mechanisms, and limitations of each approach, and finally put forward the concerns left and the possible solutions for the commercialization of LMR cathodes.",
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      "text": "Owing to the rapid population growth, energy shortage has become one of the most urgent problems to be solved. One promising strategy is to use clean energies which is renewable and environmentally friendly to replace fossil fuels [1-3]. Renewable energies like wind and solar are intermittent in nature, and they need to be collected and released using high-efficiency energy storage systems [4]. Lithium ion batteries (LIBs), considering the high energy density and long cycle life, have been widely utilized in electric vehicles (EVs) and consumer electronics like mobile phones and laptop computers [5]. Growing deployment of LIBpowered EVs reduces the emission of CO2, contributing to the mitigation of global warming. Nevertheless, the extensive application of LIBs, especially in the fields of EVs and grid-level energy storage, continues to demand for a higher energy density [6]. The energy density of LIBs largely depends on the electrode materials, especially the cathode materials. In the past decades, layered LiCoO2",
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      "text": "(LCO), spinel LiMn2O4 (LMO), olivine LiFePO4 (LFP), and LiNi x Mn y -Co z O2 (NMC, x + y + z = 1) have been the major cathode materials in LIB market [7-17]. The first-generation cathode material is LCO, which was first introduced in 1980 [18]. LCO has a high theoretical capacity (about 274 mA h g \u0000 1 ), although only half of which (140 mA h g \u0000 1 ) could be reversibly utilized during practical cycling [7,8]. The second-generation cathode materials include spinel LMO [19], olivine LFP [20], and layered NMC [21]. LMO has been widely utilized in power tools due to the superb cycling stability and low cost, however, its further development is limited due to the low theoretical capacity (148 mA h g \u0000 1 ) and even lower practical capacity (110 mA h g \u0000 1 ) [9]. LFP cathode has been adopted in EVs in recent years. LFP exhibits a high cycling stability, high rate performance, and superior abuse tolerance due to the unique P-O covalent bond [10]. The low energy density and low tap density restrict LFP cathode from a broader market [11,12]. Compared to LFP cathode, NMC cathode has been applied in EV market more effectively and fruitfully. Ni, Mn, and Co elements work coordina-",
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      "text": "Fig. 2. (a) Initial charging-discharging profiles of Li2MnO3, LiNi0.5Mn0.5O2 and Li1.2Ni0.2Mn0.6O2. (b) The 1st and 2nd CV curves of Li1.2Ni0.2Mn0.6O2 in (a). Reproduced from Ref. [35] with permission from American Chemical Society. (c) p DOS of O 2 p orbitals and Mn 3 d orbitals in Li2MnO3 and the corresponding oxygen environment model. Reproduced from Ref. [47] with permission from Springer Nature. (d) Cycling performance of Li1.2Ni0.13Co0.13Mn0.54O2 synthesized by two different synthesis methods at 0.1 C in the voltage range of 2.0-4.8 V. (e) The corresponding capacity-voltage profiles of the re-synthesized Li1.2Ni0.13Co0.13Mn0.54O2 in (d). Reproduced from Ref. [53] with permission from Elsevier. (f) Schematic representation for the structural transformation of trigonal LiMO2 component ( R -3m) and monoclinic Li2MnO3 component ( C 2/ m ) in Li1.2Ni0.1Mn0.525Co0.175O2 during cycling. Reproduced from Ref. [54] with permission from American Chemical Society. (g) Selected area electron diffraction (SAED) pattern obtained along [0001] zone axis of Li1.2Co0.1Mn0.55Ni0.15O2 cathode at the charging voltage of 4.5 V. (h) Schematic diagram of TM migration in Li1.2Co0.1Mn0.55Ni0.15O2 cathode when holding at 4.5 V. Reproduced from Ref. [55] with permission from Royal Society of Chemistry.",
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      "text": "tively in NMC cathode: Ni 2+/3+ is responsible for providing capacity, Mn 4+ is for maintaining the structural stability, and Co 3+ could promote the diffusion of Li + ions [13-16]. However, the traditional NMC cathode only offers limited improvements in terms of practical capacity (<200 mA h g \u0000 1 ) [17]. The key benchmark for the nextgeneration cathode material is a higher energy density than all current materials.",
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      "text": "Since the report by Dahn et al. in 2001, Li and Mn rich (LMR) layered oxides x Li2MnO3 \u0001 (1 \u0000 x )LiMO2 (M = Mn, Ni, Co, Fe, etc.), have been regarded as the next-generation cathode material due to the high specific capacity (>250 mA h g \u0000 1 ) [22,23]. As depicted in the formula, LMR layered oxides contain two components, trigonal LiMO2 and monoclinic Li2MnO3. The Li2MnO3 component could be activated at the first charging above 4.5 V, providing a high capacity coupling with oxygen redox. In addition, manganese is much cheaper and less toxic than cobalt, which makes LMR oxides more economically attractive compared to LCO [24]. Nevertheless, LMR oxides also have a few of drawbacks. (1) The large irreversible capacity loss during the first cycle, which leads to the low initial Coulombic efficiency. (2) Voltage and capacity decay during cycling. (3) Poor rate performance due to the poor electronic conductivity of manganese-based oxide [9,25,26]. In this review, we focus on these challenges for the commercialization of LMR layered oxides and the recent progress to overcome them. In Section 2, the basic crystal structure and the electrochemical behavior of LMR oxides are introduced. In Section 3, the recent progress on overcoming challenges for LMR layered oxides are summarized. In Section 4, promising developments and future directions for LMR oxides are suggested.",
      "text_preview": "Since the report by Dahn et al. in 2001, Li and Mn rich (LMR) layered oxides x Li2MnO3 \u0001 (1 \u0000 x )LiMO2 (M = Mn, Ni, Co, Fe, etc.), have been regarded as the next-generation cathode material due to the high specific capa…",
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      "cleaned_text": "Since the report by Dahn et al. in 2001, Li and Mn rich (LMR) layered oxides x Li2MnO3 \u0001 (1 \u0000 x )LiMO2 (M = Mn, Ni, Co, Fe, etc.), have been regarded as the next-generation cathode material due to the high specific capacity (>250 mA h g \u0000 1 ) [22,23]. As depicted in the formula, LMR layered oxides contain two components, trigonal LiMO2 and monoclinic Li2MnO3. The Li2MnO3 component could be activated at the first charging above 4.5 V, providing a high capacity coupling with oxygen redox. In addition, manganese is much cheaper and less toxic than cobalt, which makes LMR oxides more economically attractive compared to LCO [24]. Nevertheless, LMR oxides also have a few of drawbacks. (1) The large irreversible capacity loss during the first cycle, which leads to the low initial Coulombic efficiency. (2) Voltage and capacity decay during cycling. (3) Poor rate performance due to the poor electronic conductivity of manganese-based oxide [9,25,26]. In this review, we focus on these challenges for the commercialization of LMR layered oxides and the recent progress to overcome them. In Section 2, the basic crystal structure and the electrochemical behavior of LMR oxides are introduced. In Section 3, the recent progress on overcoming challenges for LMR layered oxides are summarized. In Section 4, promising developments and future directions for LMR oxides are suggested.",
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      "text": "LMRoxidesaregenerallyconsideredasthecompositeofLi2MnO3 and LiMO2, therefore the formula could be written as x Li2MnO3-\u0001 (1 \u0000 x )LiMO2 (M = Mn, Ni, Co, Fe, etc.). As shown in Fig. 1(a and b) [27], Li2MnO3 belongs to monoclinic space group C 2/ m, while LiMO2 crystallizes in trigonal space group R -3m[28]. Both of them are constructed by alternately stacking Li layers and transition metal (TM) layers along c axis within the similar cubic close packed oxygen array. The major structural difference of LMR oxides from traditional layeredoxides(LCO,NMC,etc.)istheLi@Mn6 superstructureunit.As shown in Fig. 1(c), a few of peaks could be observed in the range of 20-25 ° of the X-ray diffractogram (XRD) pattern for LMR oxide, and they cannot be observed in the XRD patterns of traditional layered oxides. This special phenomenon originates from the Li@Mn6 superstructure unit shown in Fig. 1(d) [29].",
      "text_preview": "LMRoxidesaregenerallyconsideredasthecompositeofLi2MnO3 and LiMO2, therefore the formula could be written as x Li2MnO3-\u0001 (1 \u0000 x )LiMO2 (M = Mn, Ni, Co, Fe, etc.). As shown in Fig. 1(a and b) [27], Li2MnO3 belongs to mono…",
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      "cleaned_text": "LMRoxidesaregenerallyconsideredasthecompositeofLi2MnO3 and LiMO2, therefore the formula could be written as x Li2MnO3-\u0001 (1 \u0000 x )LiMO2 (M = Mn, Ni, Co, Fe, etc.). As shown in Fig. 1(a and b) [27], Li2MnO3 belongs to monoclinic space group C 2/ m, while LiMO2 crystallizes in trigonal space group R -3m[28]. Both of them are constructed by alternately stacking Li layers and transition metal (TM) layers along c axis within the similar cubic close packed oxygen array. The major structural difference of LMR oxides from traditional layeredoxides(LCO,NMC,etc.)istheLi@Mn6 superstructureunit.As shown in Fig. 1(c), a few of peaks could be observed in the range of 20-25 ° of the X-ray diffractogram (XRD) pattern for LMR oxide, and they cannot be observed in the XRD patterns of traditional layered oxides. This special phenomenon originates from the Li@Mn6 superstructure unit shown in Fig. 1(d) [29].",
      "cleaned_text_preview": "LMRoxidesaregenerallyconsideredasthecompositeofLi2MnO3 and LiMO2, therefore the formula could be written as x Li2MnO3-\u0001 (1 \u0000 x )LiMO2 (M = Mn, Ni, Co, Fe, etc.). As shown in Fig. 1(a and b) [27], Li2MnO3 belongs to mono…",
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      "text": "Although LMR oxides are composed of trigonal LiMO2 and monoclinic Li2MnO3, the arrangement of these two structures in LMR oxides is still under debate. We list some researches on understanding the structure of LMR oxides in Table 1. One argument is the composite model, namely, trigonal phase and monoclinic phase co-exist. This model has been proved by many techniques. Qiu et al. proved the co-existence of the two phases in Li1.144Ni0.136Co0.136Mn0.544O2 powder by synchrotron X-ray diffractogram (SXRD) [30]. The composite model was also observed in Li 1.2Mn0.61Ni0.18Mg0.01O2 through high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) [31]. Two",
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      "text": "independent Fe and Mn rich nanodomains in Li1.2Fe0.4Mn0.4O2 were observed by electron energy-loss spectroscopy (EELS) measurements [32]. Besides, the composite model was also supported by Li magic angle spinning (MAS) NMR, extended X-ray absorption fine structure (EXAFS) spectroscopy, and in situ surface enhanced Raman spectroscopy [33-35].",
      "text_preview": "independent Fe and Mn rich nanodomains in Li1.2Fe0.4Mn0.4O2 were observed by electron energy-loss spectroscopy (EELS) measurements [32]. Besides, the composite model was also supported by Li magic angle spinning (MAS) N…",
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      "text": "Another widely accepted model is the solid-solution model, stating that, single solid-solution phase with C 2/ m symmetry exists in LMRoxides[36].Ithasalsobeenprovedthroughmultiplecharacterization techniques. Jarvis et al. observed single-phase ( C 2/ m symmetry) Li1.2Ni0.2Mn0.6O2 with ordered Li + in TM layer by diffraction scanning TEM (D - STEM) [36]. Shunmugasundaram et al. demonstrated the (020), (110), and ( \u0000 111) crystallographic planes related with the monoclinic phase in diminished XRD patterns [37].",
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      "text": "In summary, there is no unified conclusion about the crystal structure of LMR oxides (composite or solid-solution) till now. One possible reason is that, the actual crystal structure of LMR oxides varies with the elemental compositions (especially the content of lithium) and the synthetic conditions (oxygen partial pressure, cooling rate, etc.) [38,39].",
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      "text": "In addition, structure defects are easily introduced during the synthetic process, which affects the electrochemical performance of LMR cathodes to a large extent [40]. Zhang et al. found that the quenching process during the synthesis of Li2MnO3 would lead to the formation of Mn 3+ defects, which have significant impacts on the electrochemical activation and the cycling stability [41]. Chen et al. used molten-salt method to synthesize LMR oxides, and they noticed that there was a Co- and Ni-rich spinel phase with serious anti-site defects on the particle surface, which may be a previously-neglected factor determining the structural stability [42].",
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      "text": "The electrochemical performance of cathode materials is closely related to their structures. Since LMR oxides are composed of trigonal LiMO2 and monoclinic Li2MnO3, the electrochemical property is a combination of the electrochemical behaviors of LiMO2 and Li2MnO3 to some extent. As shown in Fig. 2(a), the charging profile of Li1.2Ni0.2Mn0.6O2 can be divided into two parts, below 4.5 V and above 4.5 V [35]. It is sloping below 4.5 V, which is similar with that of LiNi0.5Mn0.5O2, indicating the deintercalation of Li + from LiMO2 component and the solid-solution behavior [43,44]. Shimoda et al. proved that this sloping part below 4.5 V was related to TM redox [45]. Above 4.5 V, a long voltage plateau is observed for Li1.2Ni0.2Mn0.6O2, a behavior similar to Li2MnO3, implying the deintercalation of Li + from Li2MnO3 component. This voltage plateau only occurs in the first cycle, and disappears in the following cycles. The CV curves of Li1.2Ni0.2Mn0.6O2 further confirm this phenomenon: a strong oxidation peak occurs around 4.5 V in the first cycle and disappears in the second cycle (Fig. 2b). The long voltage plateau corresponds to the oxygen redox, which could only be found in Li2MnO3 and LMR cathodes [46]. The oxygen redox originates from the special Li-O-Li connection in Li2MnO3 and LMR oxide, as shown in Fig. 2(c). Compared to Mn, the O 2 p states contributes more to the total DOS close to the Fermi level (0 to \u0000 2.5 eV). Especially, the states within 0 to \u0000 0.9 eV originate from the Li-O-Li configuration, which hints that the Li-O-Li configuration is the origin of the oxygen redox chemistry [47]. It has been proved that both of TM redox and oxygen redox could be found during discharging: Ni, Co, and oxygen redox occur in the voltage range of 4.8-3.5 V and Mn redox occurs in the voltage range of 3.5-2.0 V [45].",
      "text_preview": "The electrochemical performance of cathode materials is closely related to their structures. Since LMR oxides are composed of trigonal LiMO2 and monoclinic Li2MnO3, the electrochemical property is a combination of the e…",
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      "text": "AlthoughLMRoxidescouldprovidehighcapacity(>250mAhg \u0000 1 ) and energy density (>900 Wh kg \u0000 1 ), they also have a few of disadvantages hindering the commercialization. These include: 1)",
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      "text": "Journal of Energy Chemistry 61 (2021) 368-385",
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      "text": "lowinitialCoulombicefficiency(<80%);2)severecapacityandvoltage decay during long-term cycling; 3) inferior rate performance compared to that of LCO and NMC cathodes. These challenges are discussed one by one as below.",
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      "text": "As shown in Fig. 2(a), about 100 mA h g \u0000 1 of irreversible capacity could be observed during the first cycle for Li1.2Ni0.2Mn0.6O2, leading to a low initial Coulombic efficiency of 72.3%, much lower than that of NMC and LCO cathodes. The low initial Coulombic efficiency of LMR cathode is largely attributed to the electrode/electrolyte reaction in the first cycle, especially the oxygen loss. When the charge voltage is below 4.6 V, ethylene carbonate (EC), dimethyl carbonate (DMC) and etc. in the solvent would decompose into CO2 and other gases due to the oxidizing O2 2 \u0000 species at the particle surface. Differential Electrochemical Mass Spectrometry (DEMS) measurements can validate CO2 release from the surface of the active materials, which could also be observed in other layered cathodes [48]. However, while the charging voltage is higher than 4.7 V, lattice O would evolve in the form of O2, leaving vacancies in the structure. These O vacancies lead to the irreversible migration of TM ions to Li sites. Only part of the migrated TM ions can return to their original sites during discharging, which severely decreases the initial Coulombic efficiency of LMR cathode [49]. The form of the oxygen loss has also been debated before. Yin et al. analyzed the evolution of cathode electrolyte interphase (CEI) during the first cycle of the LMR cathode [50]. They found: (1) the reasons of oxygen loss were different for LMR cathodes and Li2MnO3 cathode (caused by electrochemical decomposition and chemical decomposition, respectively); (2) the formation/dissolution of CEI was accompanied with Li + extraction/ insertion; (3) the changes in the valence states of metal ions (Ni, Co, Mn) could accelerate the formation of CEI. Besides, the decomposition of the electrolyte solution at high voltage could not be negligible. The high charging voltage (4.8 V) is normally adopted to obtain high capacity for LMR cathodes by fully utilizing TM redox and oxygen redox. At such a high voltage, the electrolyte normally composed of EC, DMC, and LiPF6, would decompose, which accompanies with the surficial side-reaction and the consumption of Li + , causing the low initial Coulombic efficiency [51]. Except for the high voltage, the highly oxidizing ions O x y \u0000 , would accelerate the decomposition of LiPF6, which accompanies with the generation of HF and PO x F y z \u0000 [52]. These decomposition products would erode the electrode-electrolyte interphase, resulting in the dissolution of the transition metal ions. Continuous dissolution of the metal ions from the material further leads to a rugged surface and increased interphase impedance, which would cause rapid degradation of the electrode.",
      "text_preview": "As shown in Fig. 2(a), about 100 mA h g \u0000 1 of irreversible capacity could be observed during the first cycle for Li1.2Ni0.2Mn0.6O2, leading to a low initial Coulombic efficiency of 72.3%, much lower than that of NMC an…",
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      "cleaned_text": "As shown in Fig. 2(a), about 100 mA h g \u0000 1 of irreversible capacity could be observed during the first cycle for Li1.2Ni0.2Mn0.6O2, leading to a low initial Coulombic efficiency of 72.3%, much lower than that of NMC and LCO cathodes. The low initial Coulombic efficiency of LMR cathode is largely attributed to the electrode/electrolyte reaction in the first cycle, especially the oxygen loss. When the charge voltage is below 4.6 V, ethylene carbonate (EC), dimethyl carbonate (DMC) and etc. in the solvent would decompose into CO2 and other gases due to the oxidizing O2 2 \u0000 species at the particle surface. Differential Electrochemical Mass Spectrometry (DEMS) measurements can validate CO2 release from the surface of the active materials, which could also be observed in other layered cathodes [48]. However, while the charging voltage is higher than 4.7 V, lattice O would evolve in the form of O2, leaving vacancies in the structure. These O vacancies lead to the irreversible migration of TM ions to Li sites. Only part of the migrated TM ions can return to their original sites during discharging, which severely decreases the initial Coulombic efficiency of LMR cathode [49]. The form of the oxygen loss has also been debated before. Yin et al. analyzed the evolution of cathode electrolyte interphase (CEI) during the first cycle of the LMR cathode [50]. They found: (1) the reasons of oxygen loss were different for LMR cathodes and Li2MnO3 cathode (caused by electrochemical decomposition and chemical decomposition, respectively); (2) the formation/dissolution of CEI was accompanied with Li + extraction/ insertion; (3) the changes in the valence states of metal ions (Ni, Co, Mn) could accelerate the formation of CEI. Besides, the decomposition of the electrolyte solution at high voltage could not be negligible. The high charging voltage (4.8 V) is normally adopted to obtain high capacity for LMR cathodes by fully utilizing TM redox and oxygen redox. At such a high voltage, the electrolyte normally composed of EC, DMC, and LiPF6, would decompose, which accompanies with the surficial side-reaction and the consumption of Li + , causing the low initial Coulombic efficiency [51]. Except for the high voltage, the highly oxidizing ions O x y \u0000 , would accelerate the decomposition of LiPF6, which accompanies with the generation of HF and PO x F y z \u0000 [52]. These decomposition products would erode the electrode-electrolyte interphase, resulting in the dissolution of the transition metal ions. Continuous dissolution of the metal ions from the material further leads to a rugged surface and increased interphase impedance, which would cause rapid degradation of the electrode.",
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      "text": "The fast capacity and voltage decay of the LMR cathodes during long-term cycling is another issue. As shown in Fig. 2(d), only 85% of the initial discharging capacity is maintained after 50 cycles at 0.1 C for Li1.2Ni0.13Co0.13Mn0.54O2. Besides, a severe decay in the discharging voltage could also be observed, as shown in Fig. 2(e) [53]. The decays in both capacity and voltage are largely caused by the structural degradation in the first cycle and the following cycles. Wang et al. proposed a structural degradation model of Li1.2Ni0.1Mn0.525Co0.175O2 [54]. As shown in Fig. 2(f), due to the concurrent oxygen and lithium loss from the lattice of Li2MnO3 component in the first cycle, the layered structure is destroyed, forming a polycrystalline/amorphous matrix. Different from the Li2MnO3 component, the LiMO2 component evolves to a spinel structure at the surface during the first cycle. The formation of a spinel structure was also observed in Li1.2Co0.1Mn0.55Ni0.15O2 during the first charge through selected area electron diffraction (SAED), as shown in Fig. 2(g). The mechanism for the formation of the spinel phase was also proposed. When the voltage is held at 4.5 V, oxygen loss will occur in the form of O2, leading to the reduction of Ni 3+ /Ni 4+ to Ni 2+ due to the charge compensation. Con-",
      "text_preview": "The fast capacity and voltage decay of the LMR cathodes during long-term cycling is another issue. As shown in Fig. 2(d), only 85% of the initial discharging capacity is maintained after 50 cycles at 0.1 C for Li1.2Ni0.…",
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      "cleaned_text": "The fast capacity and voltage decay of the LMR cathodes during long-term cycling is another issue. As shown in Fig. 2(d), only 85% of the initial discharging capacity is maintained after 50 cycles at 0.1 C for Li1.2Ni0.13Co0.13Mn0.54O2. Besides, a severe decay in the discharging voltage could also be observed, as shown in Fig. 2(e) [53]. The decays in both capacity and voltage are largely caused by the structural degradation in the first cycle and the following cycles. Wang et al. proposed a structural degradation model of Li1.2Ni0.1Mn0.525Co0.175O2 [54]. As shown in Fig. 2(f), due to the concurrent oxygen and lithium loss from the lattice of Li2MnO3 component in the first cycle, the layered structure is destroyed, forming a polycrystalline/amorphous matrix. Different from the Li2MnO3 component, the LiMO2 component evolves to a spinel structure at the surface during the first cycle. The formation of a spinel structure was also observed in Li1.2Co0.1Mn0.55Ni0.15O2 during the first charge through selected area electron diffraction (SAED), as shown in Fig. 2(g). The mechanism for the formation of the spinel phase was also proposed. When the voltage is held at 4.5 V, oxygen loss will occur in the form of O2, leading to the reduction of Ni 3+ /Ni 4+ to Ni 2+ due to the charge compensation. Con-",
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      "text": "Table 2 The electrochemical performance of LMR cathodes with different morphology design reported in recent years.",
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      "text": "Fig. 3. (a) Schematic illustration of the synthetic process of Li1.2Ni0.13Co0.13Mn0.54O2 nanowires. Reproduced from Ref. [62] with permission from Elsevier. (b) Scanning electron microscope (SEM) image of x Li2MnO3 \u0001 (1x )LiMnO2 nanorods. Reproduced from Ref. [63] with permission from Elsevier. (c) Schematic illustration of the synthetic process of orthogonally arranged nanoplates. Reproduced from Ref. [64] with permission from American Chemical Society. (d) Scheme of the fabrication process of 3D hollow porous bowl-shaped Li1.2Ni0.13Co0.13Mn0.54O2 particles. Reproduced from Ref. [66] with permission from Elsevier. (e) Schematic diagram of the suppression of voltage fading through a preferred orientation (110) plane. Reproduced from Ref. [67] with permission from Royal Society of Chemistry.",
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      "text": "sidering the similar ionic radii of Ni 2+ and Li + , Ni 2+ migrates to the Li layers preferentially compared to other TM cations. Because oxygen loss occurs at the surface, severe cationic mixing would appear at the surface during the first cycle, leading to the formation of a spinel phase, as shown in Fig. 2(h) [55]. The transformation from layered structure to spinel structure in a polycrystalline/amorphous matrix will introduce stress, causing cracks and formation of pores, which are unfavorable for Li + (de)intercalation [55]. During long-term cycling, the structural degradation will propagate from the surface to the bulk, resulting in the continuous decay of capacity and voltage. Kang et al. proposed a transition metal migration model in LMR oxides, and they",
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      "text": "observed that Li + diffusion was much more sluggish during lithiation than during de-lithiation [56]. They thought that, after Li + was extracted from Li layers, TM ions would migrate into Li layers, and they could not migrate back to TM layers easily during discharge. However, as more Li + intercalate at the end of discharge, the tetrahedral lithium occupancy induced by additional lithiation would facilitate the migration of TM ions back to TM layers, leading to recovery of the layered structure. In addition, Tarascon et al. thought that oxygen redox would come along with Mn migration under 4.6 V during charge [57]. After that, O2 was released and a structurally-densified single-phase A' formed within the bulk of the materials, not only at the surface. They also found that the",
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      "text": "Fig. 4. (a) Schematic illustration of the formation of porous Li1.2Ni0.18Co0.08Mn0.54O2. Reproduced from Ref. [68] with permission from Royal Society of Chemistry. (b) Schematic illustration of the synthesizing route for 3D Li1.2Ni0.2Mn0.6O2 and the morphological evolution. Reproduced from Ref. [69] with permission from American Chemical Society. (c) SEM image of Li1.2Ni0.2Mn0.6O2 oxide. Reproduced from Ref. [70] with permission from American Chemical Society.",
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      "text": "Fig. 5. (a) Schematic illustration of ice-template coprecipitation method to synthesize Li1.2Ni0.2Mn0.6O2 with hierarchical mesopore structure. (b) The rate performance of Li1.2Ni0.2Mn0.6O2 synthesized by freeze drying (M1) and vacuum drying (M2). Reproduced from Ref. [73] with permission from American Chemical Society. (c) Schematic diagram of building nano-porous structures in Li1.144Ni0.136Co0.136Mn0.544O2. Reproduced from Ref. [74] with permission from American Chemical Society. (d) Schematic diagram to show various structure defects in Li1.143Ni0.136Co0.136Mn0.544O2. (e) TEM image to show nano-defects (stacking faults and cationic mixing) in the Li1.143Ni0.136Co0.136Mn0.544O2. (f) Comparison for the average voltage of highly crystalline Li1.143Ni0.136Co0.136Mn0.544O2 cathode (Pristine-LrLO) and defect abundant sample (NDA-LrCO-5) during cycling at 0.1 C. Reproduced from Ref. [75] with permission from Elsevier. (g) Schematic diagram of the element gradient distribution in LMR cathodes. (h) SEM image of Li1.2Mn0.44Co0.04Ni0.32O2 with element gradient distribution and (i) EDS line scanning along the marked line in (h). Reproduced from Ref. [80] with permission from Elsevier.",
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      "text": "capacity loss in the first cycle could be recovered by applying a constant-voltage step during discharge. Li + would occupy the tetrahedral sites to form a new P'' phase under a harsh reductive condition (<1.4 V), and those Mn ions in Li layers triggered by oxygen redox would serve as ''pillars' to stabilize the structure.",
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      "text": "Another issue for LMR oxides is the unsatisfactory rate performance. This inferior rate performance can be related to the sluggish dynamics of Mn 4+ . It has been reported that Mn 4+ showed slower reaction kinetics in LMR oxides compared to Ni 2+ andCo 3+ . Although the Li2MnO3 component has been activated in the first charging process, the reaction kinetics of Mn 4+ is not promoted [25]. On the other hand, the reaction kinetics of Mn 4+ in LiMO2 component is also slow, whichcouldbepromotedbyexchangingMn 4+ byNi 2+ orCo 3+ [58]. In addition, elemental segregation of Ni and Co at the particle surface tends to take place during the synthesis process, and it also inhibits therateperformance.TheseLi + diffusion channelswithinthesurface layer are perpendicular to those in the bulk, leading to a virtual barrier in the diffusion path for Li + at the surface [59].",
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      "text": "3. Recent progress on promoting the electrochemical performance of LMR cathodes",
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      "text": "To accelerate the commercialization of LMR cathodes, researchers devoted a lot of efforts to optimize the electrochemical performance through different methods. Fortunately, the three concerns discussed above have been resolved to some extent in recent years. In this section, we will elaborate on these effective methods in three categories: morphology design, bulk design, and surface modification.",
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      "text": "Various morphologies, such as 1D nanowires, 1D nanotubes, 2D nanoplates, 3D porous morphology and other hierarchical nano morphologies, have been widely reported in other layered oxides, including LCO and NMC [60,61]. It is also an effective way to optimize the electrochemical performance of LMR oxides, such as mitigating the capacity and voltage degradation during cycling. The detailed electrochemical performance of LMR cathodes with different morphologies reported in recent years are shown in Table 2.",
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      "text": "Cathode materials with nano morphology have better Li + diffusion kinetics by shortening the transportation path, thus better rate performance. Deng et al. synthesized Li1.2Ni0.13Co0.13Mn0.54O2 spinel/layered nanowires with porous structures via a coprecipitation method followed by the controlled calcination steps, as shown in Fig. 3(a) [62]. They found that the content of spinel phase could be easily tuned by changing the heating rate. The nanowires could provide a better connection between the cathode and the electrolyte, which facilitates Li + diffusion and restrains the structural degeneration. Thus, the cathode displays a high capacity of 291 mA h g \u0000 1 at 0.1C and an excellent capacity retention of 91.8% after 200 cycles at 1C. As shown in Fig. 3(b), Yang et al. used hydrothermally synthesized b -MnO2 nanorods as a self-template to fabricate x Li2MnO3 \u0001 (1x )LiMnO2 nanorods with the diameter of 100-200 nm and the length of 400-1000 nm [63]. Increasing the fraction of Li2MnO3 could significantly increase the discharge capacity but lower the cyclic stability, while increasing the fraction of LiMnO2 could enhance the cyclic stability by suppressing the transformation from layered phase to spinel phase. As shown in Fig. 3(c), Xu et al. constructed Li1.2Mn0.52Ni0.2Co0.08O2 oxide with (010)-oriented nanoplates [64]. This novel morphology not only combines the advantages of exposed (010)-planes and the anisotropic Li + transport tunnels for fast Li + (de)intercalation, but also effectively inhibits the volume expansion during the cycling. The cathode exhibits an initial discharge capacity of 303 mA h g \u0000 1 with",
      "text_preview": "Cathode materials with nano morphology have better Li + diffusion kinetics by shortening the transportation path, thus better rate performance. Deng et al. synthesized Li1.2Ni0.13Co0.13Mn0.54O2 spinel/layered nanowires …",
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      "cleaned_text": "Cathode materials with nano morphology have better Li + diffusion kinetics by shortening the transportation path, thus better rate performance. Deng et al. synthesized Li1.2Ni0.13Co0.13Mn0.54O2 spinel/layered nanowires with porous structures via a coprecipitation method followed by the controlled calcination steps, as shown in Fig. 3(a) [62]. They found that the content of spinel phase could be easily tuned by changing the heating rate. The nanowires could provide a better connection between the cathode and the electrolyte, which facilitates Li + diffusion and restrains the structural degeneration. Thus, the cathode displays a high capacity of 291 mA h g \u0000 1 at 0.1C and an excellent capacity retention of 91.8% after 200 cycles at 1C. As shown in Fig. 3(b), Yang et al. used hydrothermally synthesized b -MnO2 nanorods as a self-template to fabricate x Li2MnO3 \u0001 (1x )LiMnO2 nanorods with the diameter of 100-200 nm and the length of 400-1000 nm [63]. Increasing the fraction of Li2MnO3 could significantly increase the discharge capacity but lower the cyclic stability, while increasing the fraction of LiMnO2 could enhance the cyclic stability by suppressing the transformation from layered phase to spinel phase. As shown in Fig. 3(c), Xu et al. constructed Li1.2Mn0.52Ni0.2Co0.08O2 oxide with (010)-oriented nanoplates [64]. This novel morphology not only combines the advantages of exposed (010)-planes and the anisotropic Li + transport tunnels for fast Li + (de)intercalation, but also effectively inhibits the volume expansion during the cycling. The cathode exhibits an initial discharge capacity of 303 mA h g \u0000 1 with",
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      "text": "Journal of Energy Chemistry 61 (2021) 368-385",
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      "text": "a Coulombic efficiency of 93%. After 200 cycles at 1C, it still has an excellent capacity retention of 92%. Similarly, Xu et al. synthesized a hierarchical quasi-spherical Li1.2Ni0.2Mn0.6O2 oxide with active (010)-oriented surface [65]. Combining the hierarchical structure and active (010)-planes, this material exhibits efficient transports of both Li + ions and electrons.",
      "text_preview": "a Coulombic efficiency of 93%. After 200 cycles at 1C, it still has an excellent capacity retention of 92%. Similarly, Xu et al. synthesized a hierarchical quasi-spherical Li1.2Ni0.2Mn0.6O2 oxide with active (010)-orien…",
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      "cleaned_text_preview": "a Coulombic efficiency of 93%. After 200 cycles at 1C, it still has an excellent capacity retention of 92%. Similarly, Xu et al. synthesized a hierarchical quasi-spherical Li1.2Ni0.2Mn0.6O2 oxide with active (010)-orien…",
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      "text": "In addition, a three-dimensional architecture with more free space between primary particles is another way to improve the cycling stability, since the volume expansion can be accommodated during cycling. Zhang et al. built 3D hollow porous bowlshaped Li1.2Ni0.13Co0.13Mn0.54O2 particles by a soft template method, and the detailed synthetic process is shown in Fig. 3(d) [66]. The material with this unique structure exhibited a high capacity of 300.9 mA h g \u0000 1 at the current density of 20 mA g \u0000 1 . No evident morphological damage could be observed even at a high current density of 400 mA g \u0000 1 , enabling its superb rate performance. This 3D hollow bowl-shaped architecture facilitates electrolyte penetration, ensuring sufficient contact between the cathode and electrolyte. The packing density was also increased via excluding the redundant space. Li et al. designed a threedimensional fusiform hierarchical micro/nano Li1.2Ni0.2Mn0.6O2 with preferentially orientated (110) planes through a hydrothermal method (Fig. 3e) [67]. The cathode not only delivered an enhanced rate performance and cycling stability, but also suppressed the voltage decay through the special triangular frame, which could prevent secondary particles from pulverization and ensure the uniform element distribution. The capacity retention achieved 94% after 100 cycles at 0.1C, and no evident voltage decay could be observed. It also delivered a high capacity of 166.8 mA h g \u0000 1 at a high rate of 5C. As shown in Fig. 4(a), He et al. used a self-made template to construct a 3D porous Li1.2Ni0.18Co0.08Mn0.54O2 cathode with an in situ modified surface [68]. This 3D porous structure with a surface modified by carbonaceous compounds, not only increased Li + conductivity, but also protected the active material from side reactions with the electrolyte. Thus, the phase transformation from layered to spinel as well as the voltage decay could be suppressed. Li et al. synthesized a 3D reticular Li1.2Ni0.2Mn0.6O2 cathode material using ordered mesoporous silica as the template [69]. The detailed preparation process and morphological evolution could be seen in Fig. 4(b). This oxide exhibited a high capacity of 195.6 mA h g \u0000 1 at 1C with the capacity retention of 95.6% after 50 cycles. The unique morphology of the material provides nanoscale Li + pathways, mechanical stability, and easy access for Li + to the center of the particle.",
      "text_preview": "In addition, a three-dimensional architecture with more free space between primary particles is another way to improve the cycling stability, since the volume expansion can be accommodated during cycling. Zhang et al. b…",
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      "text": "Design and construction of special morphologies is also a novel and efficient approach to improve the electrochemical performance of electrode materials. As shown in Fig. 4(c), Oh et al. prepared Li1.2Ni0.2Mn0.6O2 in 10 l m-sized secondary particles, which were composed of submicron flake-shaped primary particles [70]. The cathode exhibited a high capacity of 242 mA h g \u0000 1 at 0.1C and displayed a favorable cycling stability with a capacity retention of 93% after 600 cycles at 1C. Similarly, Yu et al. constructed the ball-in-ball hollow Li1.2Ni0.13Co0.13Mn0.54O2 microspheres via the co-precipitation method by tuning the nucleation, growth, and heterogeneity of the crystals [71]. The cathode showed excellent electrochemical performance with a high capacity of 193 mA h g \u0000 1 at 3C and a capacity retention of 87.6% after 400 cycles. Zhang et al. fabricated a peanut-like hierarchical micro/nano Li1.2Ni0.18Co0.08Mn0.54O2 via the solvothermal method [72]. This oxide, with better crystallinity and larger specific surface area than the counterparts, delivered a discharge capacity of 229.9 mA g h \u0000 1 at 1C and a capacity retention of 94.2% after 100 cycles.",
      "text_preview": "Design and construction of special morphologies is also a novel and efficient approach to improve the electrochemical performance of electrode materials. As shown in Fig. 4(c), Oh et al. prepared Li1.2Ni0.2Mn0.6O2 in 10…",
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      "cleaned_text": "Design and construction of special morphologies is also a novel and efficient approach to improve the electrochemical performance of electrode materials. As shown in Fig. 4(c), Oh et al. prepared Li1.2Ni0.2Mn0.6O2 in 10 l m-sized secondary particles, which were composed of submicron flake-shaped primary particles [70]. The cathode exhibited a high capacity of 242 mA h g \u0000 1 at 0.1C and displayed a favorable cycling stability with a capacity retention of 93% after 600 cycles at 1C. Similarly, Yu et al. constructed the ball-in-ball hollow Li1.2Ni0.13Co0.13Mn0.54O2 microspheres via the co-precipitation method by tuning the nucleation, growth, and heterogeneity of the crystals [71]. The cathode showed excellent electrochemical performance with a high capacity of 193 mA h g \u0000 1 at 3C and a capacity retention of 87.6% after 400 cycles. Zhang et al. fabricated a peanut-like hierarchical micro/nano Li1.2Ni0.18Co0.08Mn0.54O2 via the solvothermal method [72]. This oxide, with better crystallinity and larger specific surface area than the counterparts, delivered a discharge capacity of 229.9 mA g h \u0000 1 at 1C and a capacity retention of 94.2% after 100 cycles.",
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      "text": "In summary, the positive effects of nanoscale morphology design can be summarized as below: (1) shortening Li + diffusion pathway and increasing rate capacity; (2) releasing the strain from",
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      "text": "Fig. 6. (a) XRD patterns of Li1.2Ni0.13Co0.13Mn0.54O2 and Li1.17Na0.03[Ni0.13Co0.13Mn0.54]O2. (b) The cycling performance of Li1.2Ni0.13Co0.13Mn0.54O2 and Li1.17Na0.03[Ni0.13Co0.13Mn0.54]O2 at the current density of 100 mA g \u0000 1 . Reproduced from Ref. [84] with permission from Royal Society of Chemistry. (c) Schematic diagram of pristine LMR, LMR with surface-doped with Na (Na-LMR) and LMR with homogenously Na doping (Na/SDS-LMR) before cycling and after 200 cycles. Reproduced from Ref. [85] with permission from Wiley-VCH. (d) Schematic illustration for the structure of Mg-doped Li1.4Mg0.1[Mn0.75Ni0.25]O2+ r . (e) The rate performance of Mg-doped Li1.4Mg0.1[Mn0.75Ni0.25]O2+ r . Reproduced from Ref. [88] with permission from Royal Society of Chemistry. (f) Schematic diagram of Na and F co-doping in Li1.2Ni0.2Mn0.6O2 cathode. (g) The cycling performance of Li1.2Ni0.2Mn0.6O2 cathode (LNMO), Na doped LNMO cathode (Na-LNMO), F doped LNMO cathode (F-LNMO) and Na and F co-doped LNMO cathode (Na&FLNMO) at 0.1 C in the voltage range of 2.0-4.8 V. Reproduced from Ref. [95] with permission from Elsevier.",
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      "text": "Fig. 7. (a) Schematic diagram of Al2O3 coated Li1.2Ni0.20Co0.08Mn0.52O2. (b) The capacity-voltage profiles of Al2O3 coated Li1.2Ni0.20Co0.08Mn0.52O2 in different cycles. Reproduced from Ref. [102] with permission from Elsevier. (c) Schematic illustration of different oxygen migration model in bare and SnO2 coated Li1.2Ni0.13Co0.13Mn0.54O2 (filled with oxygen vacancies at the surface). Reproduced from Ref. [103] with permission from Elsevier. (d) Schematic diagram for the surficial structure of AlPO4 coated LMR oxide. (e) The Coulombic efficiency of the LMR oxides coated with different ALD cycles of AlPO4 during long-term cycling. Reproduced from Ref. [104] with permission from Elsevier.",
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      "text": "is another effective method to improve the electrochemical performance of LMR oxides. We will elaborate on it in Section 3.3.",
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      "text": "In addition, since O3-type LMR cathodes suffer severe voltage and capacity decay, synthesizing O2-type LMR cathodes is also an effective remedy. Xia et al. prepared an O2-type Li-rich material with a single-layer Li2MnO3 superstructure via ion exchange [83]. Owing to this novel structure, this oxide could maintain stable oxygen redox reactions and small structural changes during cycling, and delivered an extraordinary reversible capacity of 400 mA h g \u0000 1 .",
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      "text": "Fig. 8. (a) Illustration of the Li3PO4 coating process at the surface of Li1.2Ni0.2Mn0.6O2 through annealing at different temperatures. (b) TEM image of Li3PO4 coating layer. Reproduced from Ref. [107] with permission from Elsevier. (c) The cycling performance of the Li1.2Ni0.13Co0.13Mn0.54O2 cathode coated with different contents of Al2O3 and polyacene at 0.2 C (APL is short for double-shelled of Al2O3 and polyacene, and the number represents different amount of polyacene). Reproduced from Ref. [115] with permission from Royal Society of Chemistry. (d) Schematic diagram of the detailed synthetic process of the LMR cathode coated with a sandwich-like carbon@spinel@layered@spinel@carbon shell. Reproduced from Ref. [116] with permission from Elsevier. (e) Cycle performance of uncoated Li1.2Ni0.13Co0.13Mn0.54O2 (LR) and Mg2TiO4 coated Li1.2Ni0.13Co0.13Mn0.54O2 (LR@MTO) at 2 C. Reproduced from Ref. [117] with permission from John Wiley and Sons.",
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      "text": "Bulk doping has been widely reported as a traditional but effective method to improve the electrochemical performance of cathodes in LIBs, and it has also been widely applied in LMR cathodes (Table 4).",
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      "text": "Elements in the third period like Na and Mg, have been widely adopted for bulking doping. He et al. successfully introduced Na ions in the lattice of Li1.2Ni0.13Co0.13Mn0.54O2 through a polymer pyrolysis method [84]. Owing to the larger radius of Na + , Li slab became thicker while Na + replaced Li + in Li layers. As shown in Fig. 6(a), (003) peak for Li1.17Na0.03[Ni0.13Co0.13Mn0.54]O2 is located at a lower angle compared to that for Li1.2Ni0.13Co0.13Mn0.54O2, implying the increase of Li slab due to Na + substitution. Na doping successfully enhanced the structural stability and Li + diffusivity. Thus, Na-doped cathode exhibited better cycling stability compared to undoped counterpart, and it retained 89% of the capacity after 100 cycles at the current density of 100 mA g \u0000 1 (Fig. 6b). He et al. used sodium dodecyl sulfate as a surfactant, and homogenously introduced Na + in the layered lattice of Li1.2Ni0.13Co0.13Mn0.54O2, as shown in Fig. 6(c) [85]. Different from the previous reports [86], the introduction of Na + caused abundant defects in the form of stacking faults in the lattice. These stacking faults",
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      "text": "enhanced the structural stability of Li1.2Ni0.13Co0.13Mn0.54O2 cathode, which displayed better cycling stability. Du et al. performed the similar experiments [87]. Interestingly, Na ions have not been introduced to the layered lattice. By contrast, a two-phase composite formed with a new Na0.7MnO2.05 phase. Li + diffused rapidly within the boundaries between these two phases, and composite cathode got superior rate performance (130 mA h g \u0000 1 at 5 C). Mg doping can also greatly improve electrochemical performance. Yu et al. synthesized a novel cathode material Li1.4Mg0.1[Mn0.75Ni0.25] O2+ r with uniform Mg doping through coprecipitation and high temperature solid state sintering [88]. They found that, Mg ions were prone to take Li sites (4 h), as shown in Fig. 6(d). The Mg dopant has a distinct effect on promoting Li + diffusivity, which evidently improved the rate performance. As shown in Fig. 6(e), Li1.4Mg0.1[Mn0.75Ni0.25]O2+ r cathode exhibits a discharge capacity of 130 mA h g \u0000 1 at 10 C, which is much higher than that of Li1.5[Mn0.75Ni0.25]O2+ r cathode. It has also been reported that, the improved cycling stability of LMR cathode by Mg doping could be explained by the reduced charge transfer resistance and the expansion of the unit cell [89,90]. Besides, TM cations are also selected to improve the performance of LMR cathodes, such as Ti, Fe, Ru, etc. [91-94].",
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      "text": "Fig. 9. (a) Schematic illustration of the detailed process of GO modified at the surface of Li1.2Ni0.13Co0.13Mn0.54O2 cathode and the following heat treatment. (b) HRTEM image and the corresponding FFT of the layered Li1.2Mn0.54Ni0.13Co0.13O2 oxide in the bulk and the spinel structure at the surface after GO modification. Reproduced from Ref. [118] with permission from Royal Society of Chemistry. (c) The synthetic scheme of chemical adsorption to modified MoO2S2 at the surface of LMR cathode and the corresponding structure at each step. (d) HRTEM and the corresponding FFT and refined lattice images of the MoO2S2 modified LMR cathode. Reproduced from Ref. [119] with permission from American Chemical Society.",
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      "text": "Fig. 10. (a) HAADF-STEM image of the Zr-modified Li1.2Ni0.13Co0.13Mn0.54O2 cathode along [100] zone axis and the corresponding atomic models. (b) The cycling performance of Zr-modified Li1.2Ni0.13Co0.13Mn0.54O2 cathode and un-modified cathode at C/3. (c) HAADF-STEM image of the Zr-modified Li1.2Ni0.13Co0.13Mn0.54O2 cathode after 100 cycles along [100] zone axis and the corresponding atomic models. Reproduced from Ref. [122] with permission from American Chemical Society. (d) XRD patterns of Li1.2Ni0.16Mn0.56Co0.08O2 samples doped by different Al contents. (e) The average voltage of the Li1.2Ni0.16Mn0.56Co0.08O2 cathode doped by different Al contents during cycling at 0.1 C. Reproduced from Ref. [124] with permission from John Wiley and Sons.",
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      "text": "in Fig. 6(f) [95]. The Na and F dopants worked synergistically in the Li1.2Ni0.2Mn0.6O2 cathode. Na doping partly restricted the forming of spinel structure during cycling, and F doping increased the ionic and electronic conductivity. Thus, co-doped Li1.12Na0.08Ni0.2Mn0.6O1.95F0.05 exhibited excellent cycling stability and rate performance, much better than the undoped Li1.2Ni0.2Mn0.6O2 and the samples only doped by Na or F element alone (Fig. 6g). Cation co-doping has also been reported by Wynn et al [96]. Co and Mo cations co-doped in Li1.2Ni0.2Mn0.6O2, in which the degradation of capacity and voltage were successfully suppressed during cycling. This could be attributed to the modified distribution of oxygen charge density by Mo doping, which changed the local band structure and impeded the formation of oxygen vacancy, making oxygen redox more reversible. Other co-doping methods for LMR",
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      "text": "cathodes like metal ions and nonmetallic ions co-doping have also been reported recently [97,98].",
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      "text": "Surface modification is another effective way to improve the performance of LMR oxides, which includes surface coating, surface doping, and other special surface treatment.",
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      "text": "Al2O3 has been widely adopted in LMR cathodes as one of the most popular coating materials due to the material availability and various coating routes. Xu et al. coated highly crystalline Al2O3 on Li1.2Ni0.20Co0.08Mn0.52O2 through the hydrolysis of aluminum isopropoxide [102]. As shown in Fig. 7(a), three different regions formed from the surface to the bulk: the outer surface region for Al2O3 coating layer, the surface region for LiM1x Al x O2/ LiMO2 (M = Ni, Co, Mn) solid solution, and the bulk region for Li1.2Ni0.20Co0.08Mn0.52O2. On one hand, Al2O3 coating layer reduced the contact area between the electrode and electrolyte, which suppressed cation dissolution to a large extent. On the other hand, the formed LiM1x Al x O2/LiMO2 hierarchical structure prohibited the phase transformation at the surface. Nearly no capacity or voltage decay was observed in Al2O3 coated Li1.2Ni0.20Co0.08Mn0.52O2 cathode during long-term cycling (Fig. 7b). Chen et al. successfully coated SnO2 at the surface of Li1.2Ni0.13Co0.13Mn0.54O2 cathode with a uniform thickness of 4-8 nm [103]. The coating layer limited the side reactions between the electrode and electrolyte, producing a thin solid electrolyte interface (SEI) and enhancing the rate performance. In addition, oxygen vacancies were introduced by the SnO2 coating layer, which was beneficial to oxygen migration in the coating layer (Fig. 7c). Thus, the activation of Li2MnO3 in Li1.2Ni0.13Co0.13Mn0.54O2 cathode was promoted during the charging-discharging process, increasing the initial capacity.",
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      "text": "moted initial Coulombic efficiency, AlPO4 coating was also reported to improve the capacity stability [105,106]. Li3PO4 is another phosphate candidate for surface coating. Lee et al. synthesized Li1.2Ni0.2Mn0.6O2 with a thin Li3PO4 coating layer [107]. The coating was prepared during the synthesis of Li1.2Ni0.2Mn0.6O2, as illustrated in Fig. 8(a). As shown in Fig. 8(b), a thin Li3PO4 coating layer could be observed in TEM image, and it enhanced the rate performance of Li1.2Ni0.2Mn0.6O2. The same coating layer has also been achieved in Li1.2Ni0.13Co0.13Mn0.54O2 by polydopamine template method, which enhanced the cycling and rate performance [108].",
      "text_preview": "moted initial Coulombic efficiency, AlPO4 coating was also reported to improve the capacity stability [105,106]. Li3PO4 is another phosphate candidate for surface coating. Lee et al. synthesized Li1.2Ni0.2Mn0.6O2 with a…",
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      "text": "Surface coating using fluorides, organic polymers, layered and spinel oxides etc. for LMR cathodes, have also been widely reported in recent years [109-113]. Zhang et al. successfully coated AlF3 at the surface of Li1.2Ni0.15Co0.10Mn0.55O2cathode. The AlF3 enhanced the structural stability and restricted the formation of the spinel structure at the surface, effectively suppressing the voltage decay during long-term cycling [111]. Pan et al. constructed a Li x TM3x O4-type spinel shell in Li1.2Ni0.13Co0.13Mn0.54O2 oxide by in situ electrochemical activation [114]. They found that this special spinel coating could slow down the activation of Li2MnO3 and alleviate the oxygen loss and Mn dissolution, suppressing the harmful structural degradation. Zhang et al. synthesized Li1.2Ni0.13Co0.13Mn0.54O2 with a thin polyimide (PI) layer coated at the surface through polyacrylic acid (PAA) precursor, which improved the cycling stability and rate capability [109]. Multiple-layer coating could combine the function of individual coating layer together. Xu et al. designed a mesoporous Al2O3/polyacene double-shell at the surface of Li1.2Ni0.20Co0.08Mn0.52O2. They found that the best electrochemical performance was achieved when the coating was with 5 wt% of polyacene, and 98% of capacity retention could be obtained at 0.2 C after 100 cycles (Fig. 8c) [115]. Peng's group synthesized a sandwich-like carbon@spinel@layered@spinel@carbon shell at the surface of LMR cathode through a facile template-free method (Fig. 8d) [116]. Owing to the special shell structure, the as-prepared sample",
      "text_preview": "Surface coating using fluorides, organic polymers, layered and spinel oxides etc. for LMR cathodes, have also been widely reported in recent years [109-113]. Zhang et al. successfully coated AlF3 at the surface of Li1.2…",
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      "cleaned_text": "Surface coating using fluorides, organic polymers, layered and spinel oxides etc. for LMR cathodes, have also been widely reported in recent years [109-113]. Zhang et al. successfully coated AlF3 at the surface of Li1.2Ni0.15Co0.10Mn0.55O2cathode. The AlF3 enhanced the structural stability and restricted the formation of the spinel structure at the surface, effectively suppressing the voltage decay during long-term cycling [111]. Pan et al. constructed a Li x TM3x O4-type spinel shell in Li1.2Ni0.13Co0.13Mn0.54O2 oxide by in situ electrochemical activation [114]. They found that this special spinel coating could slow down the activation of Li2MnO3 and alleviate the oxygen loss and Mn dissolution, suppressing the harmful structural degradation. Zhang et al. synthesized Li1.2Ni0.13Co0.13Mn0.54O2 with a thin polyimide (PI) layer coated at the surface through polyacrylic acid (PAA) precursor, which improved the cycling stability and rate capability [109]. Multiple-layer coating could combine the function of individual coating layer together. Xu et al. designed a mesoporous Al2O3/polyacene double-shell at the surface of Li1.2Ni0.20Co0.08Mn0.52O2. They found that the best electrochemical performance was achieved when the coating was with 5 wt% of polyacene, and 98% of capacity retention could be obtained at 0.2 C after 100 cycles (Fig. 8c) [115]. Peng's group synthesized a sandwich-like carbon@spinel@layered@spinel@carbon shell at the surface of LMR cathode through a facile template-free method (Fig. 8d) [116]. Owing to the special shell structure, the as-prepared sample",
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      "text": "delivered a high initial Coulombic efficiency of 89.7% and superb cycling stability, which was demonstrated by a high capacity of 228.3 mA h g \u0000 1 after 200 cycles. Chen et al. employed inverse spinel-structured Mg2TiO4 coating to suppress oxygen evolution in Li1.2Ni0.13Co0.13Mn0.54O2 oxide [117]. This dielectric coating, through creating a reverse electric field at the surface, effectively restrained the outward migration of oxygen anions. The high oxygen-affinity elements Mg and Ti could also stabilize the surface oxygen via enhancing the energy barrier for the oxygen release. Compared to the unmodified counterpart, the modified electrode showed a superb capacity retention of ~ 81% after 700 cycles at 2C, as shown in Fig. 8(e).",
      "text_preview": "delivered a high initial Coulombic efficiency of 89.7% and superb cycling stability, which was demonstrated by a high capacity of 228.3 mA h g \u0000 1 after 200 cycles. Chen et al. employed inverse spinel-structured Mg2TiO4…",
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      "cleaned_text_preview": "delivered a high initial Coulombic efficiency of 89.7% and superb cycling stability, which was demonstrated by a high capacity of 228.3 mA h g \u0000 1 after 200 cycles. Chen et al. employed inverse spinel-structured Mg2TiO4…",
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      "text": "In addition to these common surface coating, carbon coating or molten salt were also utilized. Carbon coating with a high electric conductivity can improve the electric contact between the particles, thus decreasing the polarization during chargingdischarging. Song et al. wrapped graphene oxide (GO) at the surface of sol-gel synthesized Li1.2Ni0.13Co0.13Mn0.54O2 oxide using a simple chemical approach and subsequent thermal annealing, as shown in Fig. 9(a) [118]. Most interestingly, spinel structure formed at the surface during annealing, which could be observed in HRTEM shown in Fig. 9(b). The modified Li1.2Ni0.13Co0.13Mn0.54O2 cathode displayed a high discharge capacity of 313 mA h g \u0000 1 at the current density of 12.5 mA g \u0000 1 and 201 mA h g \u0000 1 at the current density of 2500 mA g \u0000 1 , better than most of the LMR cathodes reported before. The superior rate performance could be attributed to the synergistic effect of the GO coating, the formed spinel structure during annealing, and the recrystallized particles at the surface of the primary particles. Guo et al. used molten MoO2S2 to treat the surface of LMR cathode through a novel chemicaladsorption method, and the detailed process is shown in Fig. 9(c) [119]. A continuous and uniform surface modification layer was obtained since Mo-S and Mo-O bonds in MoO2S2 could flexibly rotate and well connect with TM cations at the surface. Then, the thiomolybdate adsorption layer induced the formation of a spinel structured layer during subsequent annealing, which could provide extra pathways for Li + and electron diffusion (Fig. 9d). Meanwhile, the MoO3 \u0000 x (SO4) x shell formed after MoO2S2 modification, which could suppress the decomposition of electrolyte and inhibit TM dissolution. Therefore, the modified LMR cathode displayed an increased capacity of 225 mA h g \u0000 1 at the current density of 100 mA g \u0000 1 , and showed nearly no capacity decay after 100 cycles. Other molten salt modifications have also been reported in recent years, such as Na2S2O8 andLiTaO3 [120,121].",
      "text_preview": "In addition to these common surface coating, carbon coating or molten salt were also utilized. Carbon coating with a high electric conductivity can improve the electric contact between the particles, thus decreasing the…",
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      "cleaned_text": "In addition to these common surface coating, carbon coating or molten salt were also utilized. Carbon coating with a high electric conductivity can improve the electric contact between the particles, thus decreasing the polarization during chargingdischarging. Song et al. wrapped graphene oxide (GO) at the surface of sol-gel synthesized Li1.2Ni0.13Co0.13Mn0.54O2 oxide using a simple chemical approach and subsequent thermal annealing, as shown in Fig. 9(a) [118]. Most interestingly, spinel structure formed at the surface during annealing, which could be observed in HRTEM shown in Fig. 9(b). The modified Li1.2Ni0.13Co0.13Mn0.54O2 cathode displayed a high discharge capacity of 313 mA h g \u0000 1 at the current density of 12.5 mA g \u0000 1 and 201 mA h g \u0000 1 at the current density of 2500 mA g \u0000 1 , better than most of the LMR cathodes reported before. The superior rate performance could be attributed to the synergistic effect of the GO coating, the formed spinel structure during annealing, and the recrystallized particles at the surface of the primary particles. Guo et al. used molten MoO2S2 to treat the surface of LMR cathode through a novel chemicaladsorption method, and the detailed process is shown in Fig. 9(c) [119]. A continuous and uniform surface modification layer was obtained since Mo-S and Mo-O bonds in MoO2S2 could flexibly rotate and well connect with TM cations at the surface. Then, the thiomolybdate adsorption layer induced the formation of a spinel structured layer during subsequent annealing, which could provide extra pathways for Li + and electron diffusion (Fig. 9d). Meanwhile, the MoO3 \u0000 x (SO4) x shell formed after MoO2S2 modification, which could suppress the decomposition of electrolyte and inhibit TM dissolution. Therefore, the modified LMR cathode displayed an increased capacity of 225 mA h g \u0000 1 at the current density of 100 mA g \u0000 1 , and showed nearly no capacity decay after 100 cycles. Other molten salt modifications have also been reported in recent years, such as Na2S2O8 andLiTaO3 [120,121].",
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      "text": "Although surface coating is one effective method to promote the electrochemistry, there are still some concerns during practical operations. (1) The uniformity of the coating. A uniform and thorough coating can effectively protect the active materials. Unfortunately, processing routes which can guarantee the uniformity, like ALD, can complicate the synthesis procedures and increase the cost. (2) The thickness of the coating materials. In consideration of the intrinsic inertness, a thick coating may inhibit the electron and Li + transport, and decrease the capacity and rate. (3) The binding force between the coating layer and the active material. The coating layer may fall off due to the volume change of cathode materials during cycling if the binding force is weak. High temperature calcination usually can improve the binding force. In brief, an ideal surface coating is a uniform coating with an optimized thickness and excellent binding force, and it should be implemented through a facile route.",
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      "text": "Surface doping is an effective way to improve electron and ion conductivity (Table 6). Li et al. synthesized Li1.2Ni0.13Co0.13Mn0.54O2 through a coprecipitation method and performed Zr surface doping",
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      "text": "Journal of Energy Chemistry 61 (2021) 368-385",
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      "text": "using a wet chemical method [122]. They found Zr element distributedwithinathicknessof1-2nmfromthesurface,andthislayer appeared in the form of rock-salt structure, as shown in Fig. 10(a). The modified sample exhibited better cycling stability compared to un-modified one, and it could retain 83% of the initial capacity after 100 cycles at 1/3C, as shown in Fig. 10(b). The promoted cycling properties could be attributed to the rock-salt structure formed at the surface, which could inhibit the formation of spinel phase during the first cycling. As shown in Fig. 10(c), no spinel structure could be observed in the modified Li1.2Ni0.13Co0.13Mn0.54O2 cathode after 100 cycles. Al doping has been reported as another effective way to promote the performance of LMR cathodes [123]. Nayak et al. doped Li1.2Ni0.16Mn0.56Co0.08O2 (Fig. 10d) with different contents of Al element and found that Li1.2Ni0.16Mn0.51Al0.05Co0.08O2 exhibited the best electrochemical performance [124]. The cooperation of Al element at the surface and in the bulk could be accomplished at this ratio, and it not only decreased the impendence but also stabilized the bulk structure. As shown in Fig. 10(e), the voltage decay was also effectively suppressed during long-term cycling. Furthermore, surface modifications of LMR cathodes using nickel and potassium elements have also been reported in previous studies, all of which exhibited better electrochemical performance compared to the unmodified LMR cathodes [125,126].",
      "text_preview": "using a wet chemical method [122]. They found Zr element distributedwithinathicknessof1-2nmfromthesurface,andthislayer appeared in the form of rock-salt structure, as shown in Fig. 10(a). The modified sample exhibited b…",
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      "text": "In addition to cation doping, anion doping is another route for enhancing LMR cathodes. One of the most widely reported doping elements is fluorine, which has also been widely used to dope others layered cathodes [127,128]. Lin et al. found that, after the surface F doping, the cyclic stability was greatly enhanced, delivering a capacity retention of 93.6% after 100 cycles at 1C [129]. Though surface F doping, Yang et al. demonstrated that the formation of vicious LiF in the SEI layer was suppressed, and thus stabilizing the electrode/electrolyte interface [130]. Breddemann et al. successfully doped F element in Li1.15Ni0.20Co0.11Mn0.55O2 by introducing fluorine gas [131]. They discovered that the rate performance of F-doped LMR cathode was closely related to the F doping content, and it was improved with a low content of F element. This might be attributed to that, the effect of F element only occurred at the surface, and too much F would decrease Li + diffusivity in the bulk. Polyanion doping has also been reported recently, and it could also promote the electrochemical performance of LMR cathode to varied extents [132,133].",
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      "text": "Erickson et al. synthesized a LMR material with ammonia surface modification [134]. Co and Mn reduction in the bulk and the formation of LiOH, Li2CO3, and Li2O at the surface (due to removal of Li-ion from the bulk) could be observed in the ammonia modified LMR cathode. In addition, the structure rearrangement occurred in the bulk of ammonia modified LMR cathode, and it reduced the coordination number of Co-O and Mn-O bonds, inhibiting the forming of spinel phase. Therefore, the ammonia modified LMR cathode exhibited superior capacity and voltage retention, much better than the un-modified LMR cathode. Similar work has also been reported by Zhang et al., who applied a surface nitridation treatment to Li1.17Ni0.25Mn0.58O2 [135]. The nitridation treatment was accomplished by heating Li1.17Ni0.25Mn0.58O2 at 400 ℃ in the ammonia atmosphere. A trace amount of nitrogen was detected at the surface by XRD, SEM, TEM and X-ray photoelectron spectroscopy (XPS). Owing to the high electrocatalytic activity of nitrogen, the discharge capacity, rate capability, and cycling stability were simultaneously promoted. The modified cathode exhibited a discharge capacity of 255.5 mA h g \u0000 1 and nearly no capacity decay was observed after 60 cycles at the current density of 30 mA g \u0000 1 .",
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